JP2007108630A - Toner for electrostatic image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a toner for electrostatic image development capable of acquiring satisfactory low-temperature fixability and a wide fixing temperature range and giving a good high-definition image. <P>SOLUTION: The toner for electrostatic image development for use in development of an electrostatic latent image, such as an electrophotographic process, an electrostatic recording process or an electrostatic printing process is obtained by dispersing in an aqueous medium an organic liquid phase prepared by dissolving or dispersing a composition for toner containing at least a compound having an active hydrogen group, a polymer having a moiety capable of reacting with an active hydrogen group, a colorant and a release agent in an organic solvent, or an organic liquid phase prepared by dissolving or dispersing a composition for toner containing at least part of the above compound, polymer, colorant and release agent in an organic solvent; bringing the compound having an active hydrogen group and the polymer having a moiety capable of reacting with an active hydrogen group into a reaction; removing the organic solvent after or during the reaction; and carrying out washing and drying, wherein the composition for toner contains a polyfunctional isocyanate compound having a molecular weight of ≤1,000. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner for developing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography and electrostatic recording, and a developer using the toner.

  Image formation by electrophotography is disclosed in Patent Document 1 (US Pat. No. 2,297,691), Patent Document 2 (Japanese Patent Publication No. 49-23910) and Patent Document 3 (Japanese Patent Publication No. 43-24748). In general, an electrical latent image is formed on a photoconductor produced using a photoconductive substance by various means, and then the latent image is developed using a developer. After development, an image formed by the developer is transferred to paper or the like as necessary, and further fixed by heating, pressurization, solvent vapor, or the like.

  Methods for developing electrical latent images can be broadly divided into liquid development methods that use a liquid developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, and a powder cloud. There is a dry development method using a dry developer (hereinafter referred to as toner) prepared by dispersing a colorant such as carbon black in a natural or synthetic resin as in the method, etc., and in recent years, the dry development method has been widely used. .

  As a fixing method used in the dry development method, a heating heat roller method is widely used because of its energy efficiency. In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner during fixing tends to be small. The 1999 DEM (Demand-side Management) program of the International Energy Agency (IEA) has a technology procurement project for next-generation copiers, and the required specifications have been published. For copiers of 30 cpm and above, It is required to achieve dramatic energy saving compared to conventional copying machines so that the standby time is within 10 seconds and the standby power consumption is 10 to 30 watts or less (differs depending on the copying speed). One method for achieving this requirement is to reduce the heat capacity of a fixing member such as a heated heat roller to improve the temperature responsiveness of the toner, but it is not fully satisfactory.

In order to achieve the above-mentioned requirement and minimize the waiting time, it is considered that it is an essential technical achievement matter to lower the fixing temperature of the toner itself and to lower the toner fixing temperature when it can be used.
In order to cope with such low-temperature fixing, an attempt has been made to use a polyester resin that is excellent in low-temperature fixability and relatively good in heat-resistant storage stability in place of the styrene-acrylic resin that has been widely used in the past (Patent Document 4: JP-A-60-90344, Patent Document 5: JP-A-64-15755, Patent Document 6: JP-A-2-82267, Patent Document 7: JP-A-3-229264, Patent Document 8: JP-A-3-41470, Patent Document 9: JP-A-11-305486).
In addition, for the purpose of improving the low-temperature fixability, an attempt to add a specific non-olefinic crystalline polymer into the binder (Patent Document 10: Japanese Patent Laid-Open No. 62-63940), an attempt to use a crystalline polyester (patent Document 11: Japanese Patent No. 2931899), but it cannot be said that the molecular structure and molecular weight are optimized.
Further, even if these conventionally known techniques are applied, it is impossible to achieve the specifications of a DSM (Demand-side Management) program, and it is necessary to establish a low-temperature fixing technique that is further advanced than the conventional technical field.

  For further low-temperature fixing, it is necessary to control the thermal characteristics of the resin itself. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated, and the resin is reduced by reducing the molecular weight. If the F1 / 2 temperature is lowered too much, there are problems such as lowering the hot offset occurrence temperature. Therefore, by controlling the thermal characteristics of the resin itself, it has not been possible to obtain a toner that has excellent low-temperature fixability and a high hot offset occurrence temperature.

On the other hand, toner production methods used for electrostatic image development are roughly classified into a pulverization method and a polymerization method.
In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and uniformly dispersed in the thermoplastic resin described above, and the resulting composition is pulverized and classified to produce a toner. ing. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, toner weight The average particle size must be reduced, and fine powder with a particle size of 4 μm or less and coarse powder with a particle size of 15 μm or more must be removed by classification, which has the disadvantage that the toner yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. Such dispersion adversely affects toner fluidity, developability, durability, image quality, and the like.
In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method or an emulsion polymerization aggregation method (Patent Document 12: Japanese Patent No. 2537503). It is.

  However, in these production methods, a polyester resin superior in low-temperature fixability cannot be used as a toner. In order to solve these problems, a toner obtained by sphering a toner made of a polyester resin with a solvent in water (Patent Document 13: Japanese Patent Laid-Open No. 9-34167) or a toner using an isocyanate reaction (Patent Document 14) : Japanese Patent Laid-Open No. 11-149180) and the like have been proposed, but the low-temperature fixability and the ability to prevent hot offset are simultaneously satisfied, and the toner productivity cannot be satisfied.

US Pat. No. 2,297,691 Japanese Patent Publication No.49-23910 Japanese Patent Publication No.43-24748 JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 Japanese Patent No. 2537503 JP-A-9-34167 JP-A-11-149180

  The present invention relates to an electrostatic image developing toner used for developing an electrostatic latent image such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method, and more specifically, sufficient low-temperature fixability and a wide fixing temperature range. It is an object of the present invention to obtain a toner for developing an electrostatic charge image capable of establishing a high-definition image.

The present inventors diligently studied for the purpose of obtaining a toner that has excellent low-temperature fixability, anti-offset performance, and good high-definition images. The present invention has been made based on this.
That is, according to the present invention, the above problem is solved by the following (1) to (11).
(1) “An organic liquid phase obtained by dissolving or dispersing a toner composition containing at least a compound having an active hydrogen group and a polymer having a site capable of reacting with the active hydrogen group, a colorant, and a release agent, Alternatively, an organic liquid obtained by dissolving or dispersing a toner composition containing at least one part of a compound having an active hydrogen group, a polymer having a site capable of reacting with the active hydrogen group, a colorant, and a release agent. The phase is dispersed in an aqueous medium, and the organic solvent is removed after or while reacting the compound having the active hydrogen group and the polymer having a site capable of reacting with the active hydrogen group, A toner obtained by washing and drying, wherein the toner composition contains a polyfunctional isocyanate compound having a molecular weight of 1000 or less "
(2) “The toner for developing an electrostatic charge image according to item (1), wherein a weight ratio of the polyfunctional isocyanate compound to the polymer is 2 to 10%”
(3) “Toner for developing electrostatic image according to item (1), wherein the polyfunctional isocyanate compound has 2 to 4 isocyanate functional groups”
(4) “The toner for developing an electrostatic charge image according to any one of (1) to (3) above, wherein the toner particles have a glass transition point of 40 to 70 ° C.”
(5) The electrostatic charge image according to any one of (1) to (4), wherein the toner particles have a BET specific surface area of 1.0 to 6.0 m ² / g. Toner for development "
(6) “The toner for developing an electrostatic charge image according to any one of (1) to (5) above”, wherein the toner particles have a volume average particle diameter of 3 to 8 μm.
(7) The above-mentioned item (1), wherein the ratio (Dv) / (Dn) of the number average particle diameter (Dn) to the volume average particle diameter (Dv) of the toner particles is 1.25 or less. Thru | or the toner for electrostatic image development in any one of (6) "
(8) The electrostatic image developing toner according to any one of (1) to (7), wherein the toner particles have an average circularity of 1.00 to 0.90. "
(9) "The electrostatic charge developing toner according to any one of (1) to (8) above, wherein the toner particles have an acid value of 0.5 to 40 mgKOH"
(10) “The toner for developing an electrostatic charge image according to any one of (1) to (9) above, wherein the toner binder resin has a glass transition point of 30 to 65 ° C.”
(11) The toner for developing an electrostatic charge image according to any one of (1) to (10) above, wherein the toner binder resin has an acid value of 1 to 50 mgKOH

  As will be understood from the following detailed description, according to the present invention, a low-temperature fixing toner having better initial printing quality and excellent image quality stability in continuous printing is provided as compared with the prior art. An extremely excellent effect is possible.

The present invention is described in further detail below.
An organic liquid phase obtained by dissolving or dispersing a toner composition containing at least a compound having an active hydrogen group and a polymer having a site capable of reacting with the active hydrogen group, a colorant, and a release agent in an organic solvent. Or an organic compound obtained by dissolving or dispersing a toner composition containing at least one part of a compound having an active hydrogen group, a polymer having a site capable of reacting with the active hydrogen group, a colorant, and a release agent. The liquid phase is dispersed in an aqueous medium, and the organic solvent is removed after reacting or reacting the compound having the active hydrogen group with the polymer having a site capable of reacting with the active hydrogen group. The toner obtained by washing and drying contains a polyfunctional isocyanate compound having a molecular weight of 1000 or less in a polymer having a site capable of reacting with the active hydrogen group, thereby satisfying low-temperature fixability and resistance. off Tsu preparative is good, and the storage stability of the toner was found to be good.

(Polymer having a site capable of reacting with an active hydrogen group)
The prepolymer (polymer having a site capable of reacting with an active hydrogen group) used in the present invention is preferably a polyester-based prepolymer (A) containing an isocyanate group, and includes a polyol (PO) and a polycarboxylic acid (PC). Polyesters having polycondensates and having active hydrogen groups can be obtained by further reacting with polyisocyanate (PIC).
In this case, examples of the active hydrogen group of the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and (DIO) alone or a mixture of (DIO) and a small amount of (TO) is preferable. Diol (DIO) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, Bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Trivalent or higher polyols (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or more polyphenols.

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and (DIC) alone and a mixture of (DIC) and a small amount of (TC) are preferable. Dicarboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene) Dicarboxylic acid and the like). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with a polyol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates are phenol derivatives, oximes, caprolactams And a combination of two or more of these.

  When obtaining a polyester-based prepolymer having an isocyanate group, the ratio of the polyisocyanate (PIC) to the polyester-based resin (PE) having active hydrogen is such that the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group are The equivalent ratio [NCO] / [OH] is usually 4/1 to 1.2 / 1, preferably 2.5 / 1 to 1.5 / 1.

  Furthermore, a polyfunctional isocyanate compound having a molecular weight of 1000 or less is added in a weight ratio of 2 to 10%, preferably 3 to 8%, more preferably 5 to 7%.

  The polyfunctional isocyanate compound to be added has 2 to 4 isocyanate functional groups. When the number of functional groups is 1, only low molecular weight components are generated, and low temperature fixability is exhibited, but a problem occurs in storage stability and the like. On the other hand, when the number of functional groups is 5 or more, a region where the urea group concentration is too high is generated locally, so that an insoluble gel is generated and low temperature fixability is not exhibited.

  As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these, or use of an adduct using these isocyanates.

(Compound having an active hydrogen group)
The most preferred compound as the compound having an active hydrogen group is a compound having an amino group. As the amine (B), polyamines and / or amines having an active hydrogen-containing group are used. In this case, the active hydrogen-containing group includes a hydroxyl group and a mercapto group. Such amines include the diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino groups (B1) to (B5). Blocked (B6) etc. are mentioned.
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), Examples include oxazoline compounds.
Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

Further, when the prepolymer (A) and the amine (B) are reacted, the molecular weight of the polyester can be adjusted by using an elongation terminator if necessary. Examples of the elongation terminator include monoamines having no active hydrogen-containing groups (diethylamine, dibutylamine, butylamine, laurylamine, etc.) and those blocked (ketimine compounds). The addition amount is appropriately selected in relation to the molecular weight desired for the urea-modified polyester to be produced.
The ratio of the amine (B) to the prepolymer A having an isocyanate group is such that the isocyanate group [NCO] in the prepolymer A having an isocyanate group and the amino group [NHx] in the amine (B) (x is 1 to 2). The equivalent ratio [NCO] / [NHx] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1. /1.2.

(Organic solvent)
In the present invention, the organic solvent for the organic liquid phase is not particularly limited as long as it is a solvent capable of dissolving and / or dispersing the toner composition. As a preferable thing, it is preferable from the point that removal is easy that the boiling point of this solvent is less than 150 degreeC. Examples of the solvent include water-insoluble water such as toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, and ethyl acetate. In addition to water-soluble or water-immiscible organic solvents, water-soluble or water-miscible organic solvents such as methyl ethyl ketone, acetone, and tetrahydrofuran can be used alone or in combination of two or more. The amount of solvent used is usually 40 to 300 parts, preferably 60 to 140 parts, and more preferably 80 to 120 parts with respect to 100 parts of the toner composition.

(Coloring agent)
As the coloring agent of the present invention, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthracene Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fayce Red, Parachlor Ortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Vulcan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Viridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin.
In addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and polymers of substitutes thereof can be used as the binder resin to be kneaded with the masterbatch or the masterbatch. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α -Methyl chloromethacrylate copolymer Styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. wear.

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method called an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 1000 cps, as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch or resin, and of course, they may be added when directly dissolving or dispersing in an organic solvent or an organic liquid phase. It may be fixed after creation.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles (toner base) obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 μm to 2 μm, and particularly preferably 5 μm to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, particularly preferably 00.01 to 2.0% by weight.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester, acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Examples thereof include polymer particles made of a resin.
Such a fluidizing agent performs surface treatment to increase hydrophobicity, and can prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, stearic acid and other fatty acid metal salts such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Circularity and circularity distribution)
It is important that the toner in the present invention has a specific shape and shape distribution. An toner having an average circularity of less than 0.90 and an irregular shape that is too far from a spherical shape exhibits satisfactory transferability and dust. A high-quality image with no image cannot be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. Toner having an average circularity of 1.00 to 0.90, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has high reproducibility with an appropriate density reproducibility. It was found to be effective for forming a clear image. This value was measured as an average circularity by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). A specific measurement method will be described later.

(Dv / Dn (ratio of volume average particle diameter / number average particle diameter))
The toner has a volume average particle diameter (Dv) of 3 to 8 μm and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.25 or less, preferably 1.10 to 1.25. The toner has excellent heat resistance, low-temperature fixability, and hot offset resistance, particularly excellent image gloss when used in full-color copiers, etc. Even if the balance is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Further, even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner layer are made thin. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, leading to a decrease in the charging ability of the carrier, When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.
On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
Further, when the volume average particle size / number average particle size is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner becomes insufficiently charged. In some cases, it was also found that the cleaning property may be deteriorated.
For the average particle size and particle size distribution of the toner of the present invention, a Coulter Counter TA-II type is used, and an interface (manufactured by Nikka Giken) that outputs number distribution and volume distribution is connected to a PC 9801 personal computer (manufactured by NEC). And measured.

(Binder resin acid value)
By setting the acid value of the polyester resin to 1.0 to 50.0 (KOHmg / g), the toner properties such as low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and charging stability are improved. Is possible. That is, when the acid value exceeds 50.0 (KOHmg / g), the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high-temperature offset resistance is affected, and when it is less than 1.0 (KOHmg / g) This is because the extension or crosslinking reaction of the modified polyester is likely to proceed, causing problems in production stability.
The acid value measuring method of the present invention is based on a method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

(Acid value of the toner itself)
According to a further study of the present invention, the toner acid value is more important than the acid value of the polyester resin for low temperature fixability and high temperature offset resistance. The toner acid value of the present invention is preferably 0.5 to 40.0 (KOHmg / g) in order to control the fixing characteristics (fixing lower limit temperature, hot offset occurrence temperature, etc.). That is, when the toner acid value exceeds 40.0 (KOHmg / g), the modified polyester is insufficiently stretched or cross-linked, affecting high-temperature offset resistance, and 0.5 (KOHmg / g). If the ratio is less than 1, the elongation or cross-linking reaction of the modified polyester is likely to proceed, causing a problem in production stability.

(Glass transition temperature of binder resin)
In the present invention, since the heat resistant storage performance of the polyester resin depends on the glass transition point of the polyester before modification, it is preferable to design the glass transition point of the polyester resin at 30 ° C. to 65 ° C. That is, if it is less than 30 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 65 ° C., it adversely affects low-temperature fixing.
The glass transition point of the present invention is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.

(Glass transition point of toner particles themselves)
The glass transition point of the toner of the present invention is preferably 40 to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. That is, when the glass transition point is less than 40 ° C., blocking in the developing machine and filming to the photoreceptor are liable to occur, and when it exceeds 70 ° C., the low-temperature fixability tends to deteriorate.

(BET non-surface area)
The toner of the present invention preferably has a BET specific surface area of 1.0 to 6.0 (m ² / g), and if the BET specific surface area is less than 1.0 (m ² / g), the presence or addition of coarse particles When the amount exceeds 6.0 (m ² / g), the image quality is likely to be affected by the presence of fine particles, the presence of additives, and surface irregularities.
The BET specific surface area of the toner of the present invention can be obtained by measuring using a device compatible with JIS standards (Z8830 and R1626) such as Tristar 3000 manufactured by Shimadzu Corporation.

(GPC)
The average molecular weight of the resin and the like was measured by GPC (gel permeation chromatography) under the following conditions.
Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min Sample: 0.1 ml injection of 0.05-0.6% concentration sample Use molecular weight calibration curve prepared from monodisperse polystyrene standard sample from molecular weight distribution of toner resin measured under the above conditions The average number molecular weight Mn of the toner was calculated.

(Measurement of NCO%)
The measuring method of NCO% is based on the method specified in JIS K1603.

The toner of the present invention can be produced by a normal pulverization method. However, since the toner exhibits the most stable performance in an environment that is not affected by shearing shear by melt kneading or temperature history by heating, the history as described above is used. It is preferably manufactured in an environment that does not receive at all.
The dry toner of the present invention can be produced by the following method, but is not limited thereto.

(Toner production method in aqueous medium)
The aqueous phase used in the present invention is used by adding resin fine particles in advance. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The toner particles are an organic liquid obtained by dissolving or dispersing a compound (A) having an active hydrogen group and a polymer (B) having a site capable of reacting with an active hydrogen group dissolved or dispersed in an organic solvent in an organic solvent. A polymer (B) having a site capable of reacting with an active hydrogen group dissolved or dispersed in an organic solvent and a compound (A) having an active hydrogen group in a dispersion obtained by dispersing a phase (oily phase) in an aqueous phase ) And are formed by reaction.
As a method for stably forming a dispersion (dispersion of [organic liquid phase] / [aqueous phase] type) obtained by dispersing an organic liquid phase (oil phase) containing the polymer (B) in an aqueous phase. Is a method in which a raw material composition liquid for a toner containing the polymer (B) dissolved or dispersed in an organic solvent (the organic liquid phase of the toner composition) is added to the aqueous phase and dispersed by shearing force. Can be mentioned. Polymer (B) dissolved or dispersed in an organic solvent and other toner composition components (hereinafter referred to as toner raw materials), colorant masterbatch, release agent, charge control agent, binder resin May be mixed when forming a dispersion of the organic liquid phase / aqueous phase, but after mixing the toner raw material in advance and dissolving or dispersing in the organic solvent, the mixture (organic liquid phase) It is more preferable to disperse in addition to the aqueous phase. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous phase. It may be added. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

  The method for dispersing the organic liquid phase in the aqueous phase is not particularly limited, and known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion made of the polymer (B) has a low viscosity and is easy to disperse.

  The amount of the aqueous phase used relative to 100 parts of the organic liquid phase of the toner composition containing the polymer (B) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic interfaces such as alkylbenzene sulfonates, α-olefin sulfonates, and phosphates as dispersants for emulsifying and dispersing the oily phase (organic liquid phase) in which the toner composition is dissolved or dispersed in the aqueous phase Activators, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts , Quaternary ammonium salt type cationic surfactants such as benzethonium chloride, nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine And Arukiru N, amphoteric surfactants such as N-dimethylammonium betaine.

  Moreover, the effect can be raised in a very small amount by using a surfactant having a fluoroalkyl group. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6 to C11). Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid And metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having fluoroalkyl groups, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzas. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries) Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble one is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. To do. It can also be removed by operations such as enzymatic degradation.

When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.
The elongation and / or crosslinking reaction time is selected depending on the structure of the site capable of reacting with the active hydrogen group of the polymer (B) and the reactivity of the compound (A) having an active hydrogen group, but usually 10 minutes. -40 hours, preferably 2-24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed.

In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferably performed in a liquid in terms of efficiency. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.
<Examples and Comparative Examples>
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10 to 15 mmHg. The mixture was reacted for 2 hours to obtain [Low molecular polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25 mgKOH.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51. Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. 15 parts of isophorone diisocyanate was added and stirred for 30 minutes to obtain [Prepolymer 1]. The isocyanate weight percent of [Prepolymer 1] was 2.07%.

~ Synthesis of MB ~
Production Example 5
1200 parts of water, 540 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained.

~ Preparation of oil phase ~
Production Example 6
In a container equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
[Example 1]
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and isophoronediamine 4.5 parts in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika) Then, 1200 parts of [Aqueous phase 1] was added to the container and mixed with a TK homomixer at a rotation speed of 13,000 rpm for 20 minutes to obtain [Emulsified slurry 1]. [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.13 μm and a number average particle size of 4.51 μm (measured with Multisizer II).
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(I): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(Ii): 100 parts of distilled water was added to the filter cake of (i), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(Iii): 100 parts of 10% hydrochloric acid was added to the filter cake of (ii), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(Iv): Add 300 parts of ion exchanged water to the filter cake of (iii), mix with TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [filter cake 1] It was. [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1].

Production Example 7
[Prepolymer 2] was obtained in the same manner as in Production Example 5 except that isophorone diisocyanate after addition in Production Example 5 was changed to 15 parts. The isocyanate weight percent of [Prepolymer 2] was 2.41%.

Production Example 8
[Prepolymer 3] was obtained in the same manner as in Production Example 5 except that isophorone diisocyanate added after production in Production Example 5; The isocyanate weight percent of [Prepolymer 3] was 2.41%.

Production Example 9
[Prepolymer 4] was obtained in the same manner as in Production Example 5 except that isophorone diisocyanate after addition in Production Example 5; 15 parts hexamethylene diisocyanate; 25 parts. [Prepolymer 4] had an isocyanate weight% of 2.71%.

Production Example 10
Post-added IPDI in Production Example 5 [Prepolymer 5] was obtained in the same manner as in Production Example 5 except that 15 parts were TDI adducts (Coronate L, manufactured by Nippon Polyurethane); 25 parts. [Prepolymer 5] had an isocyanate weight percentage of 1.81%.

[Example 2]
[Toner 2] was obtained in the same manner as in Example 1 except that [Prepolymer 2] was replaced with [Prepolymer 2] in Example 1 and 4.5 parts of isophoronediamine was changed to 5.3 parts.

Example 3
[Toner 3] was obtained in the same manner as in Example 1 except that [Prepolymer 3] was replaced with [Prepolymer 3] in Example 1 and 4.5 parts of isophoronediamine was changed to 6.0 parts.

Example 4
[Toner 4] was obtained in the same manner as in Example 1 except that [Prepolymer 4] was replaced with [Prepolymer 4] in Example 1, and 4.5 parts of isophoronediamine was changed to 5.9 parts.

Example 5
[Toner 5] was obtained in the same manner as in Example 1 except that [Prepolymer 5] in Example 1 was replaced with 3.9 parts of [Prepolymer 5] and 4.5 parts of isophoronediamine.

Production Example 10
Post-added isophorone diisocyanate in Production Example 5 [Prepolymer 6] was obtained in the same manner as in Production Example 5 except that 15 parts was changed to 0 part. The isocyanate weight percent of [Prepolymer 6] was 1.53%.

Production Example 11
[Prepolymer 7] was obtained in the same manner as in Production Example 5 except that the post-added isophorone diisocyanate in Production Example 5; The isocyanate weight percent of [Prepolymer 7] was 5.56%.

[Comparative Example 1]
[Toner 6] was obtained in the same manner as in Example 1 except that [Prepolymer 6] was replaced with [Prepolymer 6] in Example 1 and 4.5 parts of isophoronediamine was replaced with 3.2 parts.

[Comparative Example 2]
[Toner 7] was obtained in the same manner as in Example 1 except that [Prepolymer 7] was replaced with [Prepolymer 7] in Example 1 and 4.5 parts of isophoronediamine was changed to 12.1 parts.

To 100 parts of the obtained toner, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide were mixed with a Henschel mixer. The obtained toner physical property values are shown in Table 1.
Ricoh is capable of printing 45 sheets of A4-size paper per minute by preparing a developer consisting of 95% by weight of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle size of 40 μm and coated with a silicone resin. Using imagio Neo 450 manufactured, it was printed continuously and evaluated according to the following criteria.

(Evaluation item)
(A) Particle Size The particle size of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument.
(B) Circularity The average circularity can be measured by a flow particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .
(C) Tg measuring method The measuring method of Tg is outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and allowed to stand for 10 minutes, and the heating rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at / min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

<Evaluation method of characteristics>
(A) Heat-resistant storage stability After storing the toner at 50 ° C. for 8 hours, the toner was sieved with a 42-mesh sieve for 2 minutes, and the residual ratio on the wire mesh was defined as heat-resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
×: 30% or more △: 20-30%
○: 10 to 20%
◎: Less than 10% (B) Fixability A solid image of 1.0 and 1.0 on a plain paper and cardboard transfer paper (Ricoh Type 6200 and NBS Ricoh Copier Printing Paper <135>) using Ricoh's imgio Neo 450. Adjust so that the toner of ± 0.1 mg / cm ² is developed, and adjust the temperature of the fixing belt to be variable so that the temperature at which no offset occurs on plain paper and the lower limit of fixing temperature on thick paper It was measured. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
(C) Charging characteristics 1) 15 seconds stirring Q / M
Silicon resin-coated ferrite carrier (average particle size 50 μm) 100 parts 4 parts of the test toner was placed in a stainless steel pot up to 30% of the internal volume, stirred for 15 seconds at a stirring speed of 100 rpm, and determined by a blow-off method.
2) 10 minutes stirring Q / M
Charge amount when stirring for 10 minutes as in 1)

Claims (11)

An organic liquid phase obtained by dissolving or dispersing a toner composition containing at least a compound having an active hydrogen group and a polymer having a site capable of reacting with the active hydrogen group, a colorant, and a release agent in an organic solvent. Or an organic compound obtained by dissolving or dispersing a toner composition containing at least one part of a compound having an active hydrogen group, a polymer having a site capable of reacting with the active hydrogen group, a colorant, and a release agent. The liquid phase is dispersed in an aqueous medium, and the organic solvent is removed after reacting or reacting the compound having the active hydrogen group with the polymer having a site capable of reacting with the active hydrogen group. A toner for developing an electrostatic image, wherein the toner composition is obtained by washing and drying, wherein the toner composition contains a polyfunctional isocyanate compound having a molecular weight of 1000 or less. The toner for developing an electrostatic charge image according to claim 1, wherein a weight ratio of the polyfunctional isocyanate compound to the polymer is 2 to 10%. The toner for developing an electrostatic charge image according to claim 1, wherein the polyfunctional isocyanate compound has 2 to 4 isocyanate functional groups. The toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the toner particles have a glass transition point of 40 to 70 ° C. The electrostatic image developing toner according to claim 1, wherein the toner particles have a BET specific surface area of 1.0 to 6.0 m ² / g. 6. The electrostatic image developing toner according to claim 1, wherein the toner particles have a volume average particle diameter of 3 to 8 [mu] m. 7. The ratio (Dv) / (Dn) of the number average particle diameter (Dn) to the volume average particle diameter (Dv) of the toner particles is 1.25 or less. Toner for developing electrostatic images. The electrostatic image developing toner according to claim 1, wherein the toner particles have an average circularity of 1.00 to 0.90. 9. The electrostatic charge developing toner according to claim 1, wherein the toner particles have an acid value of 0.5 to 40 mgKOH. 10. The toner for developing an electrostatic charge image according to claim 1, wherein the toner binder resin has a glass transition point of 30 to 65 ° C. 10. 11. The toner for developing an electrostatic charge image according to claim 1, wherein the toner binder resin has an acid value of 1 to 50 mgKOH.